Azo phthalocyanine dyestuffs



United States Patent AZU PHTHALUCY DYESTUFFS Heinz Adolf Dortrnann,Bergisch Gladhaeh, and Peter Schmitz, Cologue-Stammheim, Germany,assignors to Farhenfahriken Bayer Aktiengesellschaft, Leverlmsen,

Germany, a corporation of Germany No Drawing; xFile'd Mar. 18, 1960,Ser. No. 16,102

I 3 Claims. ((3. 260- 147) The present invention relates to new valuabledyestuffs;

more particularly itr'elates to azo phthalocyanine dyestuffs of theformula.

to the radical R5 anybridge member.

properties.

x Pc-ER f-R N N R tR'gfRml In this formula Pc means the residuev ofaphthalo cyaninering system, R5 and R' stand for 50 and/ r (;O groups,'Rq denotes an amino group-contain- Claims priority, application GermanyMar. 21, 1959 v i ing residue of the benzene, naphthalene, pyrazolone oracylacetic acid amide series which is bound to R via the amino group, Rrepresents the residue of a diazo cornmembers containing 2 or 3 carbonatoms between N- and O or fhalogenjf halogen means C1 or Br, Rrepresents :a lower alkyleneor 'cycloalkylene radical, R5 means analkylene'radicalshaving 2 to ,3 carbon atoms between the residues R andW, R; stands for -O-- or or the grouping' Y and Z mean hydrogen oraraliphatic,"cycloaliphatic or aliphatic lsubstituent which may be aconstituent of "a I heterocyclic ring W stands for a substituent beingcapable of split offas a negative ion, q stands for one ofbthe numbersGer 1, n stands for the numbersjl to. 8 and m' component-carries atleast one grouping" Patented May 5,1964

The novelfdyestutfs' are obtained'by coupling diazo wherein Pc, R R7,R5, in and n have the above said meaning and R is any bridge'mernber,and X a hetero cyclic radical containing at least one group i chain aswell as branched alkylene residues with 2 jor 3' carbon atomsbetween' Nand -0 or .halogen.

The bridge members may also contain hetero atoms," for l instance in theease of an acyl group. Examples of resii X being an alkali metal cation,R R stand for bridge i i stands for a whole number,fwhereby the groupingcontains at leastone group" 1 His an object of the invention to providenew dyestuffs of, the'inventiongthus obtaining dyeings and dye: stuffswhich belong to the'cla ss of the sogcalled reactive dyestufis, lite.*dyestufis which are capable'to react with e l or. amide'groups offibrous material. Another; object is thesprovision of a process for thedyeing and printing of cellulosecontaining fibrous material with thenovel (R' -R)rnay also stand for a heterocyclic radical which printswhich distinguish themselves by outstanding wet fastness properties andgood to very good other fastness Further objects'will become apparentfrom the following disclosure a a 1 A 1 dues wherein R represents an-acyl' group j are the 3-chloroor bromoacetylamino or -chlor'oor-bromopropionylamjnogroup. Examples of the groupings, I

may be mentioned. as example of the residue in which 1thezeubstituentY-otZ inthe groupings i a z represents an aliphaticsubstituent which is arconstituent 3 V amides having the following Inthe Formula I the radicals R and R may be straight I (the definition ofR identical With R W. The alkylene residue R may be straight chain aswell as branched. Under the term substituent capable of being split olfas a negative ion there may be understood, for example,

ali-

ester groupings such as OSO X or El) -0 r-goxn (X being hydrogen or'analkali metal cation), sulfonyloxy groups and halogen substituents suchas C1 or Br.

Heterocyclic radicals containing the grouping v -N=( Cl which may belinked to the radical of the diazo component, for instance via primaryor secondary amino I l mine-(1,3), or N,N '2'dihydroxyethylpropylenediamrnegroups, or via sulfonamide or'carbonamidegroups or via hydroxy groups, are for instance dichloroandmonochloro-triazine, radicals as well as dichloroandmonochloro-pyrimidine radicals.

iPhthalocyanine acid amidesof the type as which are capable, of beingcoupled in the radical'R can be obtained according to the processdescribed in Belgian' patent specification 551,700 by reaction betweenphthalocyanine sulfonic acid or carboxylic acid chlorides defined and ican be carried out by various known processes via the correspondingsulfonic acid groups. Thus, sulfonic acid groups for conversion into thegrouping are reduced to the sulfinic acids or their sodium salts, theseare subjected to reaction with fi-chlorethyl alcohol or ethylene oxide,and the hydroxy groups are subsequently esterified with sulfuric acid,whereby the acid esters of sulfuric acid or their metalsalts are formed.To convert them into the groupings -S O 2N R3--R4R5W in the case where Wrepresents an -OSO X group the sulphonic acid groups in thediazocomponents containing sulphonic acid groups are transformed into thecorresponding sulphochlorides by treatment with thionyl chloride andchlorsulphonic acid, and these are condensed, preferably in a weaklyalkaline medium, with, e.g., semiesters of sulphuric acid withalkalolamines, such as ethanolamine, N-methyl Nhydroxyethylpropylenedia- (1,3). It is also possible to proceed bytransforming the sulphonic acid group into the sulphochloride group, to

react these first with alkalolamines, and eventually to esterify thehydroxyalkylsulphonarnides thus obtained with sulphuric acid ormonohydrate. In the same manand primary or secondary amines from thebenzene,

naphthalene, pyrazolone, or acylacetic acid amide series which arecapable of coupling. During this process, use may be made of metal-freeas well asmetal-containing phthalocyanines, for example those containingcopper, cobalt, nickel, iron, chromium, aluminum, or zinc.

The acid chloride groups may be located in the henzene nuclei of themacrocyclic ring or also in annellated rings or in aryl residues,whichare either linked directly to the phthalocyanine residues or viabridge atoms, such as CO, -SO or -NH,

nor, the groupings I- G Ol |TRa r 5 can .be built up from thecarboxylicacids on which they arebased. 7

Where it is desired to introduce groupings wherein W stands for ahalogen atom, the corresponding w-haloalkylamines are employed insteadof the alkanolamines for reaction with the sulphochloride or carboxylicacid The number of the formed sulfonic acid amide groups varies between1 and 8, in accordance with the number of the sulfonic acidor carboxylicacid chloride groups present inthe phthalocyanine residue. In addition,the phthalocya nine residue may also exhibit other substituents, such ashalogen, alkyl, alkoxy, or acylamino groups.

As amines which are reacted with the phthalocyanine sulfonic acid orc'arboxylic acid chlorides for the preparation of phthalocyanine acidamides, primary and secondary aromatic amines fromthe benzene,naphthalene, pyrazolone, and acylacetic acid amide series which possessin the molecule at least "one coupling position'may be employed, forexample'aminonaphthols, aminonaphthol carboxylic acid I amides,aminoarylpyrazolones,

V aminoaroylacetic acid amides, and acylacetic acid amino ar ylamides. Iv. 7

Examples of suitable diazo-cornponents for the preparation of the noveldyestuffs are aminobenzenes, aminonaphthalenes, aminodiphenyleneandaminostilbene compounds, and heterocyclic amines which contain thechloride groups. p

Coupling of the diazonium compounds with the phthalocyanine acid amidesis carried out, by the usual procedure, generally in aqueous solution,orin suspension. The dyestuffs thus obtainable'irnpart various dyeshades, according to the type of the employed azo components. The clearbluish to yellowish green dyestuffs which 'are obtained with azocomponents from the pyrazolone or acylacetic acid arylarnide series areof particular value. :1

A modified method of carrying out the process for the preparation of thenovel dyestuifs consists in first combining the diazo compoundscontaining sulphonic acid or carboxylic acid 7 groups with thephthalocyanine acid amides capable of coupling ofthe given composition,and to transform the sulphonic acidgroups into groupings of thei-formula R '+-R only after the dyestuffs have thus been obtained. In-a'similar manner, the reaction products of .diazo compounds containingsulphochloride or carboxylic acid chloride groups with alkanolarnines,for

example ethanolamines, 'may be coupled with the phthalocyanine acidamides, andthe hydroxy groups in the grouping R ,-R- at least oncewithin the molecule, f i

.The diazo components may also contain'other sub= stituents, such ashalogen, nitro, hydroxy, alkyl, alkoxy, azo, acylamino, sulfonic acid,carboxylic acid, sulfonamide, N-substituted s'u'lfo'nmnide, carboxylicacid amide, or N-substituted carboxylic acid :amide groups.

The introduction into the diazo components of the groupings -R' R havingthe definition as given above wherein R' and R represent one ofthegroupsas defined 7 above.

dyestuffs containing the hydroxyalkylsulphonamide or i-carboxylamidegroups can subsequently be esterified.

Accordingto a further modification, the novel dyestufis.

are also obtainable by introducing the grouping -SO R only into thedyestuff molecule after the diazo compounds have been coupled'with' thephthalocyanine acid amides. For this purpose, the dyestufi is subjectedto sulphochlorination, preferably with chlorsulphonic acid a and thionylchloride, whereby sulphochloride groups can also be introduced intotheJphthalocyanine molecule and intothe residue R The sulphochloridegroups can then be transformed into sulphonic orj into sulphonamidegroups p According to another embodiment of the invention the noveldyestuffs can -beobtained by condensing the acid M i l desired toprepare end products free from acid groups.

.This is of advantage in many cases, since the dyestuffs free from acidgroups yield dyeingslhaving particularly favourable wet-fastnessproperties. 1 I

The introduction into the dyestuff components of the heterocyclicgroupings X' having the definition as given above can be carried out'byvarious processes which are known per se. For instance aminogroup-containing or amide group-containing diazo components of thebenzene, naphthalene or heterocyclic series can be condensed with 2-,4,6trichloro-1,3,5-tfiazine or 2,4,6-trichloro-1,3-pyrimidine to give thecorresponding compounds containing triazinyl-amino or pyrimidinyl-aminogroups. Instead of the trichloro-triazine and trichloro-pyrimidinerespectively 7 there may'also'beused the analogous compounds having onlytwo free halogen atoms wherein the third halogen "atom is exchangedagainst any nitrogen-containing or oitygen containin'g radical such asone alkyl or arylamino radical'with or without dyestuff character, or analkyloxy or aryloxy'radical. The aforesaid exchange can, of course,

be accomplished also at other stages of the process for instance in thereaction product from the diazo component and the heterocyclic compoundor in the final phthyloc'yanine dyestuff.

The coupling of the diazonium compounds with the V phthalocyanine acidamines is carried out in usual manner. j The dyestuffs thus jobtainedshow different shades de pending on the nature of the'azo' componentused. The clear bluish green and yellowish green dyestutfs which areobtainable with the other components of the pyrazolone or acylaceticacid arylarnide series are especially valuable.

. .i A modified method of carrying; out the process forthe preparationof the novel dyestuffs according to the invention consists in firstcombining any diazo compounds con- 'taining no heterocyclicradicallwith; at least one N=oo1 group, with the phthalocyanine. acidamides capable of coupling and subsequently introducing into the radical-s thus obtained the.

of the diazo componentof the dyestu I heterocyclic radicalwith at leastone anal-e1: 3

chlorides used in .the preparationof the phthalocyanine v "acid amidesof the Formulal with 'aininoazo compounds from any diazo components'andamino group-containing coupling components of the benzene,naphthalene,*prazoioneyoi acylacetic acidarnide series and, in casediazocomponents having no heter ocyclic radical with the groupradical'oftlief diazo component. t

he phthalocyahine acidf 'amides'f may. con tain sulfonicacidfcarboiiylic,acid, or, viaany ridgiejme'mberssuch as amino and'amidegroups, hetero:-

cyclic radicals with at least one sw p;

halogen; A

The ,novel dyestuffs are; suitable for dyeing and 1 printare. used,subsequently introducing,suchla'radical intothe capable, of 1 couplingin to. other substituents such as phenyl and materials, dyeings orprints with outstanding fastness towards washing and boiling areobtained when the dyes are applied to the dyeing material and the dyeinggoods are subjected to the action of acid-binding agents, preferably at.elevated temperatures. v t

For dyeing, the dyestuffs are preferably employed in the form of anaqueous solution which can be treated with substances having an alkalinereaction, such as alkali hy: droxide or alkali carbonate, or withcompounds changing into substances with alkaline reaction, such assodium bicarbonate. Further auxiliaries may be. added to the solution,but these must not react with the dyestuffs in an undesirable manner..Additives of. this type are, for example, surface active substancessuch asalkyl sulphates,

.or compounds preventing the migration of the dyestuff,

or dyeing assistants such as urea (to improve thesolubility and fixationof the dyestuffs) or inert thickeners such as oil-in-Water emulsions,tragacanth, starch, 'alginate,or

methyl cellulose.

The solutions or pastes thus perepared-are applied .to thematerial to bedyed, for instance by padding on the foulard or-by printing, and bysubsequently heatingto an elevated temperature, preferably between .40l6C. forsome time. Heating may be carried out inthe hotflue,

steaming apparatus, or heated rollers, or by introduction.

into hot concentrated salt baths, either as a single treatment orconsecutively in any desired sequence. I

When a padding ordyeing liquor is used without alkali,

a passage of the dry material through a solution having 7 an alkalinereaction, to which common salt or Glauber salt is added, is arranged tofollow. The addition of salt during this process'reduces the migrationof dyestufi from .thefibre.

After fixing has been completed, the dyeing goodsare rinsed hot, andwhere the further use of the dyed material 'so requires, eventuallysoaped, so that residues of dye- I ate, or sodium bicarbonate, and theprinted material is rinsed and eventually soaped, Where necessary.Materials containing amide groups, such as wool, silk, syntheticpolyamide's or polurethanes andthe like can also be dyed or printed. Thedyeing process is preferably followed by a washing in aqueous liquor.

The followingexamples are given for' the purpose of c 55 illustratingthe invention:

Example 1 78.8 'pa'rts" by weight (0.05 mol) of the compound capable ofcoupling prepared by known methods from 1 mol ofnickel-phthalocyanine-(3)-tetrasulphochloride and 4 mols of l-(4'aminophenyl')3-methyl-5-pyrazolone are introduc'edinto asolution of 106parts by weight o f soda in 2 litres of water and. stirred until a.clear solution has beenobtained. 1A diazotised solutionof 0.21mi. oflaminobenzene 3 '(sulphohylamino B hydroxyethyl- "sulphuriciacid ester)is run into it at )5 C(Whil't stir ring well. After coupling iscompleted, the dyestufl is entirely salted outby addition of cornmonsalhfiltered I ,o if by suction, and dried.

0.3 part by weight of the dry dyestufi are stirred into 4 l0 of asolution rcontaining per litre parts by .weight of urea, 25 ml. ofconcentrated NaOH,and 3 ml.

ofTurkey red oil. This solution'is padded'on a cotton 7 fabric, and thisis driedat C. for.l0 minutes in a drying oven. 7 After boilingand;gsoaping, a clear neutral green dyeing is obtained, having anexcellent resistance to Wet processing and good fastness to light.

If the diazo components listed in the following table are employed inplace of the 1-aminobenzene-3-(sulphonylamino-,8-hydroxyethyl-sulphuricacid ester), valuable dyestufifs are also obtained, and these, whenfixed according to the described or modified procedure in presence of anacid-binding agent, yield on cotton the shades mentioned below:

Diazo component Shade on cotton Neutral green.

Yellowish green.

Somewhat yellowish green.

Somewhat olive tinted green.

Yellowish green.

- Neutral green.

Somewhat yellowish green. l-Aminobenzene-Z-methyl--chloro-6-(sulphonyl-Bluish green. amino-fi-hydroxyethyl sulphuric acid ester).l-Aminobenzene-2,5-dichloro-4-(sulphonylamino- B-hydroxyethyl sulphuricacid ester).

Neutral'green.

1-Arninobenzene-2,4-dimethyl-6-(sulphonylamino- Somewhat bluishfl-hydroxyethyl sulphuric acid ester). green.

l-Aminobenzene-3,4-dichloro-6-(sulphonylamino- Neutral green.

B-hydroxyethyl-sulphuric acid ester).

Example 2 195 parts by weight of 2-hydroxynaphthalenc-3-carboxylicacid-(3'-aminophenyl)-amide are stirred into 250 parts by weight ofdimethylformamide and 125 parts by weight of methanol, and 87 parts byweight of copperphthalocyanine-(3)-trisulphonic acid chloride are addedat 20-25 C. Stirring is subsequently continued at room temperature for30-40 hours, the melt is added to 750 parts by weight of methanol, themixture is filtered off by suction and washed with methanol. Forpurification the reaction product is stirredup at 60-70 C. withabout 1.5litres of dilute HCl, filtered ofi by suction, washed until neutral, anddried. The reaction product which is readily soluble in a sodiumhydroxide solution is obtained in good yield. 1 h g 0.05 mol of thephthalocyanine acid amide which is thus prepared and which is capable ofcoupling is coupled with 0.15 mol of diazotised1-amiriobenzene-3-(sulphonyl ,B-hydroxyethyl-sulphuric acid ester) in asoda alkaline solution. After coupling is completed, the pH of thesolution is adjusted to 9, and the dyestufli is entirely salted out byaddition of some potassium chloride. The dyestufi thus obtained dyescotton in brownish grey shades according to the process detailed inExample 1.

When 0.05 mol of the phthalocyanine sulphonic acid amide are coupledwith 0.15 mol of diazotised l-aminobenzene 2methoxy-4-(sulphonylamino-B-hydroxyethyl-sulphuric acid ester), thedyestufi'thus obtained dyes cotton in dull violet shades.

Example 3 0.05 mol of a compound capable of coupling and pre pared.from130 parts by weight of 1.-amino-7 hydroxy naphthalene and 87 partsby weight of copper-phthalocotton in green-blue shades according to theprocess described in Example 1.

v "When 0.05 mol of the phthalocyanine-sulphonic acid amide are coupledwith 0.15- mol of the diazotised 1'- aminobenzene- 2 me'thoxy 4(sulphonylamino- 5- hydroxyethyl-sulphuric acid-ester), the dyestufithus obtained dyes cotton in blue-grey shades.

8 Example 4 (a) 0.1 mol of the dyestuif from 4 mols of diazotisedl-aminobenzene-3-sulphonic acid and 1 mol of phthalocyanine-sulphonicacid amide, capable of coupling and prepared from 1 mol ofnickel-phthalocyanine-(3)-tetrasulphonic acid chloride and 4 mols of1-(4'-aminophenyl)-3-methyl-5-pyrazolone, is introduced into 500 ml. ofchlorsulphonic acid whilst cooling with ice. The mixture is heated to35-40 C. for 1 hour, 150 ml. of thionyl chloride are then addeddropwise, and stirring is continued for 4 hours. After cooling, therneltis added to ice, the well crystalline green sulphochloride of thedyestuff is filtered 01f by suction, and washed with ice water untilneutral to Congo red. p p

(b) 0.02 mol of the moist dyestuff sulphochloride prepared according to(a) are introduced whilst cooling with ice into an alkaline solution (pHvalue 95-10) of 28 parts by weight of ,B-aminoethyl alcohol-sulphuricacid semiester in 200 m1. ofwater. Cooling is then removed, and thetemperature is allowed to rise gradually to 20-25 C. During thisprocess, the water-insoluble sulphochloride goes into solution with agreen colour. The pH value is kept constant by addition of dilute NaOH.After condensation is completed, the dyestufi is salted out with KCl,filtered off by suction, and dried at 50 C. in vacuo.

The dyestufi thus preparedcan be applied to cotton or staple fibre bytheusual method from aqueous alkaline solutions or by means of asuitable printing paste. Green dyeings or prints are obtained, havinggood fastness to washing, light and solvents. Y

@(c) The dyestufl obtainable according to procedure (b) may also beprepared by' first condensing the sulphochloride with an aqueoussolution of fi-arninoeth-yl alcohol,

and esterifying the sulphonic acid hydroxyethyl amide with sulphuricacid or chlorsulphonic acid according to usual methods.

Example 5 a Example 6 0.0211101 of a dyestnff sulphochloride preparedaccording to Examp1e ,4a are introduced at O-5,. C. into a solutionof.27 parts by'weight of N-tnethyl-N-hydroxyethylpropylenediamine-(lfi)in 300 ml. of Walter. The temperature is allowed to rise gradually to20-25 C., stirring is continued for 2 hours, and finally heating iscarried out at C. for 2-3 hours. j The reaction product is then filteredoff by suction "Whilst hot, the residue is washed out with water, anddried at 60 C. in vacuo.

The green condensation prodpot thus-obtained is dissolved inthrere timesits amount by volume of sulphuric acid nronohydrate (5.5 its amo unt byweight) at 1 5-20 C.,' and is added to ice after stirring for 3-4 hours,

and filteredQ For removal ofl miner al acid, itis washed with ice water,the residue is adjusted to pH 6 with dilute NaOH, and dried at 50? C. invacuo.

. The dyestutf can beapplied to cotton or regenerated cellulose in theusual manner by' means ofalloalis, fixed l by means of heat treatment,and results in green dyeings or prints having good fastness propertiesto boiling, light, and solvents. *t- 1 l l l l Example 8 froyellowish-green dyeings or prints obtained according to theab'oWedescribed methods of fixation exhibit good 0.055 mol of thedyestufi' from 4 tools of diazotised 1-methyl-4-aminobenzene-2-sulphonicacid and l mol of i N the phthalocyanine-sulphonic acid amine, capableof conpling and prepared from 1 .mol of nickel-phthalocyanine-(3)-tetrasulphonic acid chloride and 4 mols of l-(4'-aminophenyl)-3-methyl-5-pyrazolone, are introduced into i I 200 ml. ofohiorsulphonic acid whilst cooling with ice.

After'istirrin-g forone hour -at'3 0 C., the dyestuif had it rinsed withwater until the filtrate running off no longer introduced at 5 C. into asoda alkaline solution of 56 l pants b-y weightiof fi arninoethylalcohol-sulphuric acid -semiester iii-560 ml. ofwater at'pH 9.5 10." ThepH 1 value is kept constant by" addition of dilute sodium aydissolved..60 ml. of thionyl chloridev are now added drop- Wise, stirring iscontinued at 30 C. for 3 hours, and themelt is added to ice To removemineral acids, it

- shows acid reaction. .The moist sulphoohlroride' is thengeneral'fastness properties.

. Example 11: a 97 parts b weight 0.1 m1 of copper-:phthalo cyanine (3)tetra-sulphonic acid chloride obtainable by.

known methods are condensed in aqueous solution (about 1.5 litres) andat room temperature with 0. 1 mol of the monoazodyestuif obtained .bycoupling diazotised 1- amino-2methoxybenzene 4 su1phonicacid.hydroxyethytlamide-snlphuric :acid semies-ter with 1-(4-aminophenyl)-3-methyl-54pynazolone, and wvith.0.31mol of (3-aminoethylalcohol-sulphuric acid sem-iester, whilst the pH value is keptconstant at 9.5-9.8. Afiter condensation is completed, the dyestufl isisolatedby salting out, filtered off by suction, and dried. According tothe above-described methods of fixation bluish green dyeings or printsare obtained on materials containing hydroxyl groups.

'lfb) When the proportions of the. reaction components in process (a)are modified as, follows:

0.1 mol of copperaphthalocyanine v(3) tetrasulphonic acid chloride;

0.2 mol of monoazodyestufi l-arninoa 2 methoxybenzene- 4-sulphonic acid'hydroxyethylamide sulphuricaoid -seiniester- 1-(4Faminophenyl) 5 3met-hyl-S-pyr-azolone,

\ 0.2 mol of o=hydroxyethylamineesulphuricacid semiester,

droxide soiution. The green condensation product thus obtained'isinsoluble in Water, but freadily dissolves in dilute alkalis with agreencolour. The dyestuff ester can he applied and fixed on cotton andviscose rayon by the methods described above.

: Example 9' "0 .1 mol of dyestuil' fromfl mols of diazotised aniiineand lmol'of phthalocyanineesulphonic acid amidej'capableof coupling andprepared from ,1 mol of nickelphthalocyam'n e g)-tetrasulphonic acidchlorideand 4 niols ioltl 1-(4'. or 3 aminophenyl) -3 methyhipyrazolone,

the dyestufl? thus obtained dyes materials containing hydroxyl groups inyellowishgreen shades; f

(c) When the proportions of the reaction component in process'm) aremodified as followsz' 0.1 mol of-copper-phthalocyanine gteitrafsulphdhic acid chloride,

-; 0.3 moliof monoazodyestutf l an iino '2 7 inetho iybenzene 4sulplionic acid-hydroxyethylamide-sulphuric V f' acid semiesterepl-"(4','- aminophenyll-fi met-hyl 5- is introduced'with cooling, at 15-20C. into 400' ml.

otf chlorsulphonic" acidf The temperature is raised to 40? C. and:stirring is continued until no more hydrogen chloride escapes. 9O ml. ofthionyl chloride are then 'addeddropwise in accordance with its rate ofconsumption. After cessationofigas evolution; the melt is added to iceand washed until free from acid; J The dyestuil f sulphoohloiideobtained is I insoluble in'water.- It

c'an beicondensed, according to the methods detailed in Examples 4-8,with ethanolainine, l-aininohenzened I sulphonicacid-hydroxyethylamide-sulphuric acid senders.-

V ter, 1-aminobenzene-3-sulplioniclacid hydroxyethylamide,-

N-methyl-N hydrogyethylpropylenediamineg( 1,3 N,N-

drateorchlorsulphonic acid/pyridine,- yielding dyestuffs which, Withtheaid of alkalis, can be applied to and fixed on fibres containinghydroxyl groups or amide groups.

The dyeings 'onprints thus obtained have good fastness properties toboiling, light, and'solyents.

In the Examples L9? by'coupling 4 mold of diaiotised l amino-2methoxybeni zenef or 1 atmino-2-methioxybenzene-4-sulphonic acid withdihydroxyethyl-propylenediamine-(1,3) or" similar hydroxyalkylamines,and here required" be transformed ,(a') 97uparts by cyani ne- (B)tetrasulphonicacidbhloride are condensed in aqueous solution (about 1.5litres) and at room temperature with 0.1 mol of the tmon'oazo-dyestufiobtained by pyrnazolone,

0.1 .molof ,6hydroxyethylaminewsulpliuric acid semiester, l the dyestuffthen obtained dyes materials containinglhydroxyl groups-in intenseyellowish 'grenshades. 1

coupling diazotisedj1-jamino*- 2 chloro ben zrene-4-sul- 1 phonicacid-hydroxyethylamidesulphuric acid semiester with '1 (3 4aminophenyl), 1.3 methyl- -;-5 ;.-v pynazolone,

v.and with 0.3 molofi-fi-aminoethylalcohol-sulphuricracid asemie ster,whilstthepI-I-value iskept constant :at 9.5-9.8. .Wlien condensation fiscompleted, the dyestuffjis isolated by salting out, filtered off.byisuction, and dried... Acc'ording to the knownjmethodsfof fination intheipresence of containing hydroxyl groups,

" (b), -When the proportions of;the-reactioniconrponents ,inpro-cessla)are modified as followsr 1 l ;0.1 meter nickel ieninaiec annteg 3y t e a30.2 mol df monoazo jdyestiif Lamina- Z -chIomben Zene-i;

Q j 4' sulphonic acid 5 hydroxyethyl amide l-sulphuric 0.2 molof.B-hydiboXythylaniihe-shlphurit; acid seniiester,

1 .molyoqf phthalocy aninesulphonici acid :arnide, capable of coupling"and,=prepared= moi of nickel-phthaio- 3 cyanine(3)-tetnasulphonicacid-chloride mois of '1- 1X 4'-amihophenyl )-3-methyl-5pyrazolone, can i be tracn-sv a m-a1" iZ-thio' chloride, and-convertedto valuable dyestuffs Wit'h irito'Lsulphochiorides :With chl ors'ulphonic fa'cid/ hols or eir sulphuric"acidifse-miestensi' The jai, x 1.groups or amide jg r oiips'ingreedfshades.-

(c) When theapi oportio S v iiiproces sihlyarempdified'asiollows: l

0.1 no hfiiicke-lphthalo cyanine a f acid chloride;

semiester 1'- s aiaind hen n lone, Y

the dyestuff then obtained dyes. rnaterialsrcontaiiiing hy acidchloride; L

of thereaotion components v z-ftetrasulphdiiic 0.3 mol ofmonoazodyestuff l-amino 2 chionobenzene- 14 sulphonic acidhydroxyethylamide sulphuric acid semiester 1-(3'-aminophenyi) 3 methyl vpyrazolone,

0.1 mol of fi-hydroxyethylamide-sulphuric acid semiester,

the dyestuft then obtained also dyes material containing hydroxyl groupsand amide groups in green shades.

Example 13 After condensation is completed, the dyestuff is isolated bysaitingout, filtered oif by suction, and dried. According to theabove-described methods of fixation, -green dyeings or prints-areobtained on materials containing hydroxyl groups.

(b) When theproportions of the reactionjcomp onents V in process (a)iare modiiied as'iolloiwsz I x 0.1 moi of copper-phthaiocyanine (3)tetr-asuiphonic acid chloride, v r j 0.2moi ot monoazo dyestufi l-amino2 chiorobenzene 4 suiphonic acid hydroxyethyiamide sulphuric acidsemiester 1-(3'-aminophenyl) 7 3 methyl 5 pyrazo- 1one,, 0.2 mol ofp-hydroxyethyiaminesuiphu ic acid semiester, the dyestufi then obtaineddyes materials-containing hydroxyl groupsin green shades.

, (c) .Wh-en the proportionsof the reaction c inprocess (a) aremodiiiedas-foliows: r

0.1 mol of copper-phthaiocyanineefi)atetnasulphonic acid chloride, I

0.3 mol of monoazodyestuff i-amino 2 chiorobenzene- 4 sulphonic acidhydrooryethyiamide sulphuric acid seiniestjare-sil-(3f-aminophenyi) 3methyl 5 -py-razolone, i

0.1 mol of B hydroxyethyiamine-sulphuric acid semiester,

been formed.

, omponents Into this susp'ension there is run in 0.2 mol of an aqueoussolution, neIutralised with sodium acetate, of the diazoniurn saitof thecondensation product prepared by known methods from 1 mol of2,4-diaminobenzene-sulfonic acid-1 and i moi of cyanuric chloride. Aftercoupling is rlinished'the dyestuif is salted out'by addition ofpotassium chloride, filtered, washed neutral with potassium chloridesolution and subsequently dried in vacuum at 25 to 30- C. The dyestuffdissolves in water and dyes ceiiulose-containingfibres a't'elevatedtemperature, for instance at 30 to 35 C. from preferably sodaaikaiinebath in clear green shades of excellent fastness to wet processing. 7

Example 16 78.7. parts by Weight (0.05 moi) of the compound capable ofcoupling and prepared by known methods from 1 mol ofnickel-phthalocyanine-(3) tetrasulfochloride and 4 mols" ofl-(4'-arninophenyi)8-methyi-pyrazolone-5 are introduced in a solution of106 parts bylweight of soda in 2.1. of :water and stirred until a clearsolution has Into this solution there are in at 0 to 5 C. a diazotisedsolution of 0.2 mol of a condensation product from 1 mol of2,4-diaminobenzene-sulfonic acid-1 and 1 mol of1-(4'-sulfophenyiamino)-3,5-diohlorotriazine. After coupling is completethe dyestuli is precipitated by addition of sodium chloride, filtered,washed neutral and dried at room temperature. The dyestufi can be paddedfrom an "alkaline bath containing sodium chloride on cellulose materialsand yields clear green shades with outstanding fastness to wetprocessing.

. Example 17 78.7 parts by weight (0.05 mol) ofthe compound capable ofcoupling and pr epared from 1 mol ofnickelphthaiocyanine-(3)-tetrasulfochloride and 4 mols of l- (4aminophenyi) 3 methyl 5; pyrazolone 5 are dissolved soda alkaline in 2to '3. l. ofwater and adjusted to a neutral or slightly acid pH value byadding acetic acid. A 7, Into this solution there are added dropwise.good stirring at 0 to 5 Cpa diazotised. solution, neutralised by theaddition of sodium acetate, of. 0.1 moi of thel-aminobenzene-3-/3-hydroxyethylsulfonesulfuricacid semiester thedyestufi then obtained dyes materials containing hydnoxyi groups ingreen shades.

f 1 wmlzl i v 97 pants by weight (0.1 moi) of m ckeLphthaiocyanine- (3tetrasulphonic acid chloride are condensed in aqeuous soiution-(about"1.5 litres) and at room'temperature with 0;imolof the monoazodyestuifobtained by coupling diazotised 1 amino-2-carboxybenzene 4suiphon-ic1acidhydnoxyethyiamidesulphuric acid semester with l-(4-am'inophenyl) 3 methyl- 5 -pyrazolone, and with 0.3 "moi offi-hydroxyethylamine-suiphumic acid semiester, whilst the pH'value iskept constant at 9.5-'-9.8. vAfter condensation iscompleted, thedyestuff'is isolated by salt- 'ing out, filtered "ofi bysncti'on, anddried. According to the above-described methods of fixation, somewhatbluish een dyeings or printsare obtainedpon materials containinghydroxyl groups.

a; When'the dyestufiis subjected to an ammonical cop g per ing,isoiation followed by the describedmethods of hydroxyl groups.

a ma s-15' 7 *7s'iibin (0.05 inoD ofthe compound capabie of couplingwhich isfobtainabie by known methods 6.5 jfirgationproduce green.dyeings orprints on materials conrideiand 4 mols of lj(4 aminophenyl) 3methyl-pyrazodilute acetate acid in a fine statq prepared by knownmethods andat the same time a diazotised' solution, neutraiised by theaddition of sodium acetate, of 0.1 mol of 1-aminobenzene 3,5-disulionicacid. When the coupling is complete the dyestufi isolated and dried invacuum at a low temperature.

By fixing for instance on cotton in the presence of acid-binding agentsby the herein described methods, clear grecn shades of outstandingfastnessto Wet processing are obtained.

I Exumple' l8g, h I

. 78.7 parts by weight (0.05 mol) of the compound capable of couplingand prepared from 1 mol of nickelphtha-lo'cyanine-(3)-tetrasulfoohloride4 mols of l- .(4 aminophenyi) 3 methyi pyrazoione 5 are dissolved sodaalk-aline in 2 .10 3 l. of water and adjusted to. a neutral orslightiyacid pH .vaiue aby the addition o f glaciaiacetic acid.- Intothis solution there is added dropwise' with good stirring'at 0 to 5 C. adiazotised solution, neutralised by the addition of sodium acetate, of0.1' moi of 1 amino-2-methoXybenzene-4di hydroxyethylsuifone-suifuricacid Jsemiesten preparedby known methods and at the same time a diazotisiedzsolution, neutra'lised by the addition ofsodium acetate of 0.1mol of 1-aminobenzene=3,5-disulfonic acid. A

Aiiter the coupling is: complete the ,dyestuff is isolated and dried invacuum yat a low temperature.

7 By fixing the dyestufffor instance on cotton in the presence a id-binn ents at e h n de cr solution, neutralised by the addition of sodium 13Example 19 78.8 parts by weight (0.05 mol) of the compound capable ofcoupling and prepared from 1 mol ofnickelphthalocyanine-(3)-tetnasulfochloride and 4 mols of 1- (4aminophenyl) 3 methyl pyrazolone 5 are dissolved soda alkaline in 2 to 3l. of water and adjusted to a neutral or slightly acid pH by addition ofglacial acetic acid.

into this solution there are added dropwise with good stirring at 0 to 5C. a diazotised solution, neutnalis'ed by the addition of sodiumacetate, of 0.1 mol of l-aminobenzene-3,5-disulfonic acid--chloroethylamine prepared by known methods and at the same time adiazotised acetate, of 0.1 mol of 1-aminobenzene-3,5+disulfonic acid.

After the coupling is complete the dyestufl is isolated and dried'invacuum at a low temperature.

By fixing the dyestufi for instance on cotton in the presence ofacid-binding agents by herein described methods clear green dyeings ofoutstanding fastness to wet processing are obtained.

What is claimed is:

1. A dyestuif which in the free acid state corresponds to the formulawherein Pc stands for a metal phthalocyanine moiety seieoted from thegroup consisting of copper phthalocyanine, nickel phthalocyanine, andcobalt phthalocyanine, R 45 SOz-NH-CHg-CH -OSO H CHa J4 3. Aphthalocyanine dyestuif corresponding to the formula References Cited inthe file of this patent UNITED STATES PATENTS 1,857,244 Hentrich ct alMay 10, 1932 2,195,390 et a1 Mar. 26, 1940 2,434,493 Muller a a1 July22, 1947 2,995,412 K161) Aug. 8, 1961 v FOREIGN PATENTS 218,807Australia Nov. 18, 1958 OTHER REFERENCES lovlllegmannz Textile Praxis,October 1958, pp. 1056-

1. A DYESTUFF WHICH IN THE FREE ACID STATE CORRESPONDS TO THE FORMULA